Novel diamidodialanes and process for the preparation thereof

ABSTRACT

A NEW CLASS OF DIAMIDODIALANES, REPRESENTD BY THE FORMULA:   X2-AL-N(-R)-(CH2)N-N(-R)-AL-X2   WHEREIN X IS HYDROGEN, HALOGEN OR A SECONDARY AMINE RADICAL; EACH R IS A HYDROCARBON RADICAL AND SAID R&#39;&#39;S, TOGETHER, ARE MEMBERS OF THE GROUP CONSISTING OF (A) A PAIR OF HYDROCARBON RADICALS THAT ARE UNLINKED DIRECTLY TO EACH OTHER, AND (B) A PAIR OF HYDROCARBONS THAT ARE LINKED DIRECTLY TO EACH OTHER TO FORM A RING; AND N IS A WHOLE NUMBER RANGING FROM 2 TO 6. THE RESEPECTIVE MEMBERS ARE USEFUL AS A COMPONENT OF A CATALYST SYSTEM IN THE POLYMERIZATION OF OLEFINS, DIOLEFINS AND POLYENES, AND MAY BE PREPARED BY A SUBSTITUTION REACTION OF A DIAMINE CHLOROHYDRATE WITH AN ALUMINUM HYDRIDE.

United States Patent NOVEL DIAMIDODIA LAI IES AND PROCESS FOR US. Cl. 260-448 R Claims ABSTRACT OF THE DISCLOSURE A new class of diamidodialanes, represented by the formula:

wherein X is hydrogen, halogen or a secondary amine radical; each R is a hydrocarbon radical and said Rs, together, arev members of the group consisting of (a) a pair of hydrocarbon radicals that are unlinked directly to eachother, and (b) a pair of hydrocarbons that are linked directly to each other to form a ring; and n is a whole number ranging from 2 to 6. The respective members are useful as a component of a catalyst system in the polymerization of olefins, diolefins and polyen'es, and may be prepared by a substitution reaction of a diamine chlorohydrate with an aluminum hydride.

The present invention refers to new aluminum compounds, to the process for the preparation of the same and to the process utilizing said compounds as components of catalyst systems in the polymerization of unsaturated compounds. Aluminum compounds are known which have been employed in the recent past in the so-called low Li 1U wherein X is H and/or halogen and R is a hydrocarbon radical.

The compounds according to the first formula and the employment of same are described in UK. Pats. Nos. 995,797; 980,773; and 979,391.

The compounds according to the second formula and 1 the employment of same are described in UK. Pat. Nos.

1,131,258; 1,131,257; 1,131,259; and 1,131,206.

The compounds according to the present invention are different both from those having the Formula 1 and from those having the Formula 2; they are quite new compounds and are very useful in the polymerization of compounds having at least one olefinie unsaturation.

3,781,318 Patented Dec. 25, 1973 ice The process for preparing the above compounds is essentially based on substitution reactions. The inventive compounds have the general formula:

in which X is hydrogen, halogen or a secondary amine radical, both Rs are hydrocarbon radicals or form a ring and R is a divalent hydrocarbon radical.

More particularly the invention refers to compounds having the formula:

in which X and R have the aforesaid meanings and n is a whole number ranging from 2 to 6.

According to current terminology, said compounds are called diamidodialanes and they will be referred to accordingly hereinafter.

The process for preparing the above compounds is essentially the following:

(1) The chlorohydrate of the suitable diamine is prepared in ether (the composition of the obtained compound is analytically verified);

(2) The amine hydrogen atoms are replaced by aluminum atoms one of which is bonded to a hydrogen atom; the other aluminum atoms may be bonded to hydrogen, to a halogen, to a secondary amine radical or to both latter compounds. The substitution is carried out by reacting the diamine chlorohydrate with hydride compounds of almninum.

When the hydride aluminum compound is LiAlH the reaction scheme is the following one:

- HzAlIII-(CHzh-lTh-AIH: 2LlC1 411;

The reaction may also be carried out by starting with diamine and AlH The synthesis of the inventive compounds may be easily carried out because it is based on the replacement of the amine hydrogen and involves a direct bond between amine nitrogen and a hydride aluminum atom. The synthesis is carried out at a temperature ranging from 20 to C. and at a pressure which is given by the vapor pressure of the solvent at the working temperature.

The solvent may be selected from the class of ethers as, for example, dimethyl ether, diethyl ether, methyl ethyl ether, cyclic ethers and mixtures of hydrocarbon with the cited ethers.

The aluminum hydride compounds are selected from I AlH both etherate and polymer, AlH ClEt o, H AlNR The other reactant is selected from the diamine compounds and the chlorohydrates of same. Examples of the latter compounds are 1,3-diethylamino-propane, NN'diethyleth'ylenediamine, NN'-dipropylethylenediamine, NN'- diethylhexamethylenediamine and 'the chlorohydrates of the same.

The so obtained inventive compounds have the above said formula: NN'-diethylenediamidodialane, NN'.-dipropylethylenediamidodialane and the like may be cited among them. They are useful as components of catalyst systems in the polymerization of compounds having at least one olefinic unsaturation. The utilization range of Solubility 'the' same is very fact they may advantageously "replace the 'iedueingcofiip'oundof a'Ziegler catalyst which notoriously consists of an aluminum metallorganic compound (reducing compound) and a transition metal compound. Therefore they are very suitable for providing catalysts having many uses and the advantages of uninflammability and the most safety.

Examples of monomers which may be polymerized are:

(a) the olefins and their mixtures;

(b) theiconjugated and unconjugated diolefinsand mixtures thereof;

(c) the polyenes and mixtures thereof.

It is also possible to co-polymerize the compounds of class (a) both with the ones of class (b) and with the ones of class The invention is now illustrated by the following unrestrictive examples:

EXAMPLES (1) 207 ml. of a 2.97 M solution of LiAlH were slowly added to 58.6 g. of chlorohydrate of NN'-diethylethyl- .enediamine (MW=189) corresponding to 620 mg. atoms of nitrogen. The reaction suddenly occurred by freeing H after the addition the solution was forced to boil at reflux for two hours. It was filtered, then the ethyl ether was eliminated by stripping and anhydrous benzene was added. All the operations were carried out in an inert and anhydrous room. The analyzed solution had the following composition:

Mmoles/ ml. of solution A1 1.32 H* (H*=hydride hydrogen) 2.48 N 1.47

Ratios:

Theoretical value: H*/Al=2; N/Al=l Found value: H*/Al=1.88; N/Al=1.12

Mmoles/ml. Al 0.97 N 1.10 1.8

Ratios:

Theoretical value: H*/Al=2; N/Al=1 Found value: H*/Al= 1.86; N/Al=1.14

mmole/cc'." (3) NN'-diethylhexamethylenediamine was utilized in a working procedure according to Examples 1 and 2. A

in cyclohexane and in n-heptane: 0.067

' compound was obtained which was soluble in ethyl ether and benzene, very active and having the following composition: Mmoles/ml. Al 0.157 N" 0.173 I, H* 0.3 1

- from which the molar ratios resulted the following ones:

1=1.97 and N /Al=1.10

(4)NN'-diisopropylethylenediamine was utilized in a working procedure according to Examples 1 and 2. A

f f' 4' compound was obtained which was soluble in ethyl ether and benzene," veg/active and having the following ratios:

Mmoles/ml. Al 0.704 N 0.750 a: 1.34

Ratios:

Theoretical value: H*/Al=2; N/Al=1 Found value: H*/Al =1.91; N/Al=1.06

POLYMERIZATION EXAMPLES: ETHYLENE (1) Two liters of anhydrous and airless n-heptane was loaded into a 4 liter autoclave provided with a turbine stirrer; it was thermostated at C., then the preformed catalyst was loaded, it consisting of 0.8 g. of TiCl AA (corresponding to 2 mmoles/1.) and of 0.34 g. of NN'- diethylethylenediamidodialane (corresponding to 4 mg. atoms/liter of H*) (TiCl AA=TiCl activated by aluminum).

Hydrogen was fed at a pressure of 3 atmospheres, it acting as molecular weight regulator, then ethylene was sent up to a total pressure of 6 atmospheres and was kept at such a value by a flow regulated by the same running of the polymerization reaction. After two hours the reaction was stopped by n-butyl alcohol; after 3 hours of digestion it was centrifuged, washed with water and acetone and then dried. 650 g. of polyethylene were obtained having d=0.959 and MFI=0.198 (MFI=Melt Flowing Index).

(2) The procedure of Example 1 was followed except for the catalyst which consisted of 0.8 g. of TiClgAA. (corresponding to 2 mmoles/l.) and of 0.35 g. of NN'- diethylpropanediamidodialane (corresponding to 4 mg. atoms/liter of H*). 450 g. of polyethylene were obtained having d=0.961 and MFI=0.249.

(3) 450 ml. of n-heptane were loaded into a 1 liter autoclave provided with a propeller stirrer; it was thermostated at 90, then the catalyst was loaded, it having been prepared starting from 0.74 g. of TiCl AA and 0.077 g. of NN'-diethylethylenediamidodialane in ml. of nheptane, corresponding to a H*/Ti ratio of 0.48.

It was pressurized by 4 atmospheres of H and 1 atmosphere of ethylene and the pressure was kept at 5 atmospheres during the whole polymerizatiomAfter 2 hoursof polymerization the pressure was removed, the catalyst was destroyed by butyl alcohol; then the polymer was filtered, washed with acetone and dried. 44 g. of polyethylene were obtained, having d=0.958 and MFI=0.18.

(4) The procedure of Example 3 was followed and a catalyst was employed which consisted of- 0.26 g. of TiCl AA and 0.16 g. of NN'-diethylethylenediamido- -dialane. 47 g. of polyethylene were obtained having d=0.960 and MFI=0.25. 1

(5) The procedure of Example 1 was followed except I for the catalyst which consisted of 4.9 mmoles of TiCl and of 2.46 mmoles of NN'-diethylethylenediamidodialane corresponding to 9.8 mmoles of H Hydrogen was fed'at a pressure: of 3 atmospheres and ethylene wasfed up to a total pressure of atmospheres, which pressure was kept constant by an ethylene flow. After two hours the polymerization reaction was stopped by-butyl alcohol, then the polymer was centrifuged, washed with water and acetone and dried. 400 g. of polyethylene were. ,obtained;,having d=0.964 and MFI=1.5.

POLYMERIILZYATIONV EXAMPLES: PROPYLENE (1) 300 ml. of anhydrous and airless n-heptane were loaded into a 750 ml. autoclave; after it had been thermostated at 40 C., the preformed catalyst was loaded, it consisting of 0.9 g. of TiCl AA and 0.17 g. of NN-diethylethylenediamidodialane into 100 cc. of n-heptane.

Propylene (Phillips) was fed at a pressure of 4 atmospheres and the pressure was kept at such a value by a propylene flow regulated by the same polymerization reaction. After two hours the reaction was stopped by an ethyl alcohol-acetone mixture, the polymer was filtered, washed with the alcohol-acetone mixture and dried at 50 C. under vacuum. 50 g. of polypropylene were obtained.

(2) The procedure of Example 1 was followed except for the catalyst which consisted of 0.9 g. of TiCl AA and 0.28 g. of NN-diethylpropanediamidodialane into 100 ml. of n-heptane. 17 g. of polypropylene were obtained.

(3) The procedure of Example 1 was followed except for the catalyst which consisted of 0.9' g. of TiCl AA, 0.27 g. of NN'-diethylethylenediamidodialane and 0.26 g. of triethylamine. 8 g. of polypropylene were obtained.

(4) The procedure of Example 1 was followed except for the catalyst which consisted of 0.9 g. of TiCl AA, 0.27 g. of NN'-diethylethylenediamidodialane and 0.2 cc. of anisole corresponding to an anisole/aluminum molar ratio of 0.5. 17 g. of polypropylene were obtained.

(5) The procedure of Example 3 was followed except for the catalyst which was used in an amount of 0.54 g. 15 g. of polypropylene were obtained.

POLYMERIZATION EXAMPLES: ISOPRENE (1) 90 ml. of anhydrous and airless hexane were loaded into a series of flasks having a 200 ml. capacity; then 1.82.10- moles of TiCl were fed with NN'-diethylenediamidodialane in such an amount so as to have the following Al/Ti ratios: 0.7, 0.8, 0.9, 1.0. The flasks were plugged; the catalyst was allowed to age for minutes, then 30 ml. of freshly distilled isoprene were added. The flasks were plugged by a crown plug and put in a thermostat kept at 30 C. All the operations were carried out in a very anhydrous vessel. After two hours the polymerization was stopped by adding ethyl alcohol and the polymer was coagulated by ethyl alcohol too. After drying the following conversions were obtained:

Conversion percent g.

Al/ Ti: dried polymer 0.7 33 .3 0.8 70.0 0.9 35.0 1.0 23.0

POLYMERIZATION EXAMPLES: COPOLYMERS (l) 2 liters of anhydrous and airless n-heptane were, loaded into a 4 liter autoclave provided with a turbine stirrer; it was thermostated at C. and then the preformed catalyst was loaded. It consisted of 0.8 g. of TiCl AA (corresponding to 2 mmoles/l.) and 0.34 g. of NN'-diethylethylenediamidodialane (corresponding to 4 1 mmoles/liter of H*).

Hydrogen was fed at a pressure of 3 atmospheres, it acting as molecular weight regulator, then ethylene and 4% by volume of propylene were sent up to a total of 6 atmospheres, and the pressure was kept at such a value by an ethylene-propylene flow regulated by the same running of the polymerization reaction.

After two hours the reaction was stopped by butyl alcohol and after 3 hours of digestion the polymer was centrifuged, washed with a water-acetone mixture and dried. 250 g. of copolymer were obtained having d=0.950 and MFI-=0.5.

What we claim is:

1. Aluminum compounds having the general formula:

in which X is hydrogen or halogen; both Rs are hydrocarbon radicals; and R is an unsaturated or saturated aliphatic divalent hydrocarbon radical, unsubstituted cycloalkyl radical, or unsubstituted aryl radical.

2. Aluminum compounds according to claim 1 having the formula:

in which X and R have the aforesaid meanings and n is a whole number ranging between 2 and 6.

3. NN'-diethylethylenediamidodialane.

4. NN-diethylpropanediamidodialane.

5. NN'-diethylhexamethylenediamidodialane.

6. NN'-diisopropylethylenediamidodialane.

7. A process for preparing aluminum compounds having the formula:

wherein X is hydrogen or halogen; both Rs are hydrocarbon radicals; and R is an unsaturated or saturated aliphatic divalent hydrocarbon radical, unsubstituted cycloalkyl radical or unsubstituted aryl radical, said process consisting of a reaction between a diamine or a diamine compound and a hydride aluminum compound which reaction is carried out at a temperature ranging between 20 C. and +70 C. and at a pressure which is given by the vapor pressure of the reaction solvent at the working temperature, the solvent being an ether, a mixture of ethers or a mixture of ethers and hydrocarbons.

8. A process for preparing aluminum compounds having the formula wherein X is hydrogen or halogen; both Rs are hydrocarbon radicals; and R is an unsaturated or saturated aliphatic divalent hydrocarbon radical, unsubstituted cycloalkyl radical or unsubstituted aryl radical, said process consisting of a reaction between a diamine or a diamine compound selected from the group consisting of 1,3-diethylaminepropane, NN-diethylethylenediamine, NN-dipropylethylenediamine, NN-diethylhexylenediamine and chlorohydrates thereof and a hydride aluminum compound which reaction is carried out at a temperature ranging between 20 C. and +70 C. and at a pressure which is given by the vapor pressure of the reaction solvent at the working temperature, the solvent being an ether, a mixture of ethers or a mixture of ethers and hydrocarbons.

9. A process according to claim 7 characterized in that the aluminum hydride compound is selected from the group consisting of (i) MeAlH in which Me is an alkaline metal, preferably Li, or All-I both being complexed by ether or (ii) A1H X complexed by ether in which X is a halogen.

10. A process according to claim 7 characterized in that ether is selected from the group consisting of dimethyl ether, diethyl ether, methylethyl ether, cyclic ether, mixtures of said ethers and mixtures of said ethers with hydrocarbons.

References Cited- Chemical Abstracts, vol. 60, 6909, 1410811-14109 Chemical Abstracts, Vol.72, 1l5335s (1970)."

Laubengayer et a1.: J. Amer. Chem. Coc., vol. 83, pp. 542-546 (1961).

Laubengayer et a1.: Inorganic Chem., vol. 1, pp. 632- 637 (1962).

10 HELEN M. S. SNEED, Primary Examiner US. 01. X.R. 

